Process of producing hydrocarbon products by the action of a metallic halide and a partially chlorinated mineral oil of the carbo-cyclic series



Dec. 20, 1932. CHAPPELL 1,891,619 PROCESS OF PRODUCING HYDROCARBON PRODUCTS BY THE ACTION OF A METALLIC HALIDE AND A PARTIALLY CHLORINATED MINERAL oIL OF THE CARBO-CYCLIC SERIES Filed'March 7. 1927 Patented Dec. 20, 1932 UNITED STATES PATENT OFFICE MARVIN L. CHAPPELL, 0F LOS ANGELES, CALIFORLIIA, .ASSIGNQR TO STANDARD OIL COMPANY OF CALIFORNIA, OF SAN FRANCISCO, CALIFORNIA, A CORPORATION OF DELAWARE PROCESS OF PRODUCING HYDROCARBON PRODUCTS BY THE ACTION OF A METALLIC HALIDE AND A PARTIALLY CHLORINATIEI) MINERAL OIL OF ZIH'E CARBO-CYCLIC SERIES Application filed March 7,

This invention relates to the treatment of mineral oils, such as petroleum oil, with metallic halides, such as aluminum or ferric chloride.

In the conventional method of reaction upon petroleum oils by metallic halides, such as aluminum chloride, the petroleum oil and metallic halide admixture is heated to a temperature of from 300 to 600 F. Particularly when the process is carried out for the production of gasoline or motor fuel, a large percentage of the high boiling point unsaturated components of the petroleum oil are polymerized with the formation of tars. The formation of such tars hinders, to a large extent, further reaction of the metallic halide on the oil and increases considerably the difficulty of securing proper contact with the metallic halide and the oil, thereby necessitating the employment of excessive amounts of a uminum chloride to treat the oil or resulting in the production of a small yield of gasoline or motor fuel.

Furthermore, when hydrocarbon oil is subjected to the action of metallic halides for the purpose of refining the oil for the production, for example, of high grade lubricating oils, the unsaturated high boiling point h drocarbons are also polymerized and are difficult to separate from the lubricating oil stock and, moreover, both increase the difiiculty of obtaining contact between the hydro carbon oil and metallic halide and also hinder the further action of the metallic halide on the oil by rendering said metallic halide less active.

I have discovered that this tar formation can be decreased and a higher percentage of motor fuel or refined oil produced by first treating the mineral or petroleum oil to be processed with chlorine under conditions to form with the unsaturated compounds of the oil, a partially chlorinated or addition product. Such a reaction has been found to proceed when such mineral or petroleum oils are treated with chlorine at a temperature ranging approximately from to 212 F. Under such conditions, suflicient chlorine combines with the unsaturated oils of the mineral oil body to form substantially satu- 1927. Serial No. 173,253.

rated chlorinated hydrocarbons. When such partially chlorinated mineral or petroleum is thereafter subjected to reaction With metallic halide, particularly in the presence of nonchlorinated compounds of saturated nature, they may be refined to produce a high grade lubricating stock with a minimum production of tar and with great efliciency insofar as the consumption of aluminum chloride is concerned.

Moreover, when such partially chlorinated mineral or hydrocarbon oils are treated with a metallic halide, particularly in the presence of non-chlorinated saturated oil at temperatures ranging from 300 to 650 F., and preferably under evolved pressure of about 20 pounds per square inch gage, a high yield of gasoline or motor fuel may beobtained with a low production of tar and a low consumption of metallic halide.

form or example of a process which embodies the 1nvent:on.

which embodies the invention. The process is described in connection with the accompanying drawing, Which illustrates diagrammatically an apparatus suitable for conducting the process.

In the drawing:

The apparatus is indicated as in diagrammatic elevation and with certain parts in vertical section.

Referring to the drawing, 2 indicates a reaction chamber preferably provided with some suitable heating means, being indicated as set over a furnace 3 provided With a burner 4. 5 indicates a line having a valve 6, which line may be employed for introducing mineral or'petroleum oil into the reaction chamber 2. The reaction chamber 2 is also provided with a line 7 controlled by a valve 8 for introducing chlorine into the reaction chamber 2, said line 7 preferably I For this purpose, I have heremafter set forth an example of a process with a vapor withdrawal line 10, controlled by a valve 11, by which means petroleum vapors and unreacted chlorine or other products may be withdrawn from the reaction chamber 2 as desired.

The reaction chamber 2 is indicated as connected by a line 12 including a pump 13 to a second reaction chamber 14. The re action chamber 14 is indicated as provided with an aluminum chloride charger 15 including the hopper 16 and spaced valves 17 and 18 by which solid metallic halide may be' introduced into the reaction chamber against the pressure employed therein. The charger is also indicated as provided with a valve controlled line 19 by which metallic halide in liquid form may be introduced if desired.

The reaction chamber 14 is preferably provided with suitable heating means and for this purpose, is indicated as mounted over a furnace 20 having the burner 21. Thereaction chamber 14 also preferably includes suitable means, such as the rotary agitator22 for agitating the contents of the reaction chamber. 23 indicates a vapor line lead'ng from the reaction chamber 14 to a dcphlegmator or reflux tower 24.

The reflux tower 24 is provided at its lower end with a line 25 which may be utilized for assing reflux or condensed materials either y line 26, controlled by valve 27, back into reaction chamber 14 or through line 28, controlled by valve 29 to a receiver 30. The receiver 30 is indicated as having a valve controlled draw-ofi line 31.

The dephlegmator 24 is preferably provided with a planer 32 having inlet and outlet passages 33 and 34 by means of which the temperature of the va ors discharged from the dephlegmator may e controlled. If desired, the oil either in line 5 or in line 12 may be pased through this planer. The dephleginator is connected with a vapor withdrawal line 35 leading through a condenser 36 to a receiving tank 37 for the gasoline or other low boiling point oil reduced in the process. Said receiving tan" 3?} is rovided with a valve controlled vent line 38 y means of which the pressure imposed upon the system may be controlled.

The reaction chamber 1% is also connected 1 with a residual withdrawal line 39 controlled lgy a valve 401 which line leads to a receiver 41 meters constituents. Within the reaction chamber 2, the mineral hydrocarbon oil and chlorine which are continuously fed therein are maintained at a temperature ranging from approximately to 212 F. and suliicient chlorine is added to substantially combine with all of the unsaturated oils to form therefrom saturated chlorinated hydrocarbon compounds. T he reaction is generally as indicated in the following equation, in which R indicates any hydrocarbon radical:

n H n n .aaamaaaas Upon certain mineral or hydrocarbon oils, a considerable portion of the chlorine fed into the reaction chamber 2 will not react with the oilsfupona single passage through the body of oils and it is understood that the same is then merely recirculated through'the body of the oil to secure eilicient use of the chlorine.

The partially chlorinated mineral or hydrocarbon oil which always contains a quantity of saturated mineral or hydrocarbon compounds which have not been chlorinated is continuously passed into reaction chamber 14 in which chamber it is subjected to reaction with a metallic halide, preferably aluminum chloride. The temperature of the reaction in the reaction chamber 14 and the relative quantities of metallic halide and partially chlorinated mineral oil fed into the reaction chamber will depend upon the kind of reaction desired to effect in said reaction chamber. The process of the presentinvention is of a vanta e in case it is desired to produce refined lu ricatin oil stock or other refined viscous stock andis also of advantage when it is'desired to conduct the metallic halide reaction to effect the catalytic decomposition of the oils into lower boiling point oils. In case a catailiytic decomposition reaction is desired to be e ected, the partially chlorinated mineral oil is heated in reaction chamber 14 to a temperature ranging from 300 to 650 F. The reaction is preferably conducted under a pressure above atmospheric, such as 20 pounds gage. As an example of suitable proportions of a metallic halide, such as aluminum chloride, I prefer to employ around 0.2 to 0.8

pounds of aluminum chloride per gallon of oil to be treated.

In case alubricating stock only is desired, a smaller amount of the metallic halide or aluminum chloride is used and a lower temperature range is generally employed. For

' LBQLMQ In case the higher temperaturesare em-.

ployed to produce motor fuel, a further reaction proceeds between the hydrocarbon formed and the metallic halide, such as indicated by the following equation:

residuum The vaporsevolved in the reaction charm ber 14 are preferably passed to the dephlegmator 24 in which the motor fuel or naphtha is separated from the higher boiling point oils and passed from the dephlegmator together with the hydrogen chloride produced,

the naphtha being condensed in the condenser 36v and collected in the receiving tank 3?. The hydrogen chloride gas is withdrawn from the vent line 38 and, of course, may be recovered in any preferred or suitable manner.

The condensed high boiling point oils with or without some vaporized and condensed metallic halide may be passed either from the dephlegmator 24 to receiver 30 for. a later separation or processing, or where it is desired to conduct the reaction to produce only naphthaor motor fuel and unrefined high boiling point oil, such condensed material from dephlegmator 24 may be passed to the evaporating chamber 14.

It will thus be seen that the process may be carried on mainly for the production of naphtha or mainly for the production of a refined viscous stock or for the simultaneous production of both naphtha and a refined viscous oil stock. In any case, the quantity of metallic halide necessary for such refining or decomposition is materially reduced over that required where the metallic halide iscontacted with a normal mineral hydrocarbon oil iii-place of the chlorinated or partially chlorinated oil employed in the present process.

It may be advantageous to employ pressures below atmospheric in certain cases, particularly when the process is being run for the production of lubricating stock.

\Vhile the process herein described is well adapted for carrying out the objects of the present invention, it is understood that numerous modifications may be made and all such modifications come withinthe scope of the following claim.

I claim:

.A process of converting mineral oils of relatively high boiling point into motor fuels, while a par-it of the oils are simultaneously polymerized into refined viscous oils which comprises first contacting the same with chlorine at a temperature sufiicient to chlorinate substantially only the unsaturated oils while separating the light petroleum vapors, and thereafter subjecting the liquid chlorinated mineral oils to reaction with a metallic halide at a temperature between 300 650 F., and at a pressure about seventy pounds per square inch above atmospheric.

Signed at Los Angeles this 28 day of Feb ruary, 1927.

MARVIN L. CHAPPELL.

CERTIFICATE OF CORRECTION Patent No. 1,891,619. December 20, 1932.

MARVIN L. GHAPPELL.

It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as fellows: Page 3, line 86, the claim, for "seventy" read "twenty"; and that the said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 16th day of May, A. D. 1933.

' (go (Seal) Acting 'G-ornn'sissiener of Patents. 

